Applications of IR Spectrometry

Qualitative and
Quantitative Analysis using
IR Spectrometer
(Session 7)
Qualitative and Quantitative Analysis
Ultimate goal of IR analysis is identification of the substance
measured or determination of its quantity.

Usefulness of the IR technique mostly lies in the Qualitative

Identification of cpds; hence more emphasize should be given to
this aspect.

Remember!
Specific bonds present in a molecule give rise to absorption
bands at specific ’s in the IR region corresponding to the
types bonds.
Qualitative analysis based on the IR makes use of information
acquired from A measurement at specific ’s to each bond
type;
The information so obtained can provide the basis for
identifying and elucidating the structure of a sample
molecule.
Applications of IR Spectra: Qualitative
Analysis
The IR spectra are generally transmission spectra:
Calibrated mostly in wave numbers (cm-1 ) or in wave length (μm);
The baseline is at the top of the chart and marks 100% T;
Thus, IR peaks emerge from top and extend down to the 0% T
level indicating max absorption (see Fig. 26 & 27).

The IR region covers the  range of about:

2.5 μm to 17 μm, or 4000 cm-1 to 600 cm-1.

IR absorption pattern for a particular molecule provides its

molecular "fingerprint" just as in the UV/vis region.

Generally, most IR absorption bands appear relatively sharper

than the UV-vis bands. Explain why?

If a particular IR band of a molecule appears to be much

sharper, it indicates the presence of a particular type of bond in
the structure.
Applications of IR Spectra: Qualitative Analysis…….

Fig. 26. The IR Spectra of Vanillin (Peaks recorded from the

Top down)
Applications of IR Spectra: Qualitative Analysis…….

Fig.27. Gas Phase IR Spectrum of Formaldehyde,

H2C=O
Applications of IR Spectra: Qualitative Analysis……

For best IR analysis:

thickness of the sample is chosen so that T should lie b/n 25% -
50%.
solution samples mostly prepared in either CCl4 or CS2 as a
solvent.

Qualitative identification of a cpd can be carried out by:

superimposing its IR spectrum and then
checking it band-to-band against the spectrum of a standard
sample (with known conc.)
If impurity is suspected, a pure sample of the impurity is
prepared and its IR spectrum is run separately, its bands are
then checked and subtracted from the original combined
spectra.

Qualitative analysis using IR when combined with GC, is now

finding wide applications in identifying easily various compounds
after being separated by the GC technique.

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Important Spectral Regions in IR
Most characteristic bands appear in the peak ID region,
which is from about 4000 cm-1 to 1500 cm-1

The long  region, from about 1500 cm-1 to 600 cm-1 is

often described as the "fingerprint" region (see next slide
Fig. 28).

The fingerprint range is mostly used to match the spectrum

of an unknown cpd. peak for peak with that of a known.

Collections of spectral data for known compounds can be

accessed from a database library resources; for example,
the Sadtler IR database library.
Fig. 28. The “Fingerprint” and “Peak ID” regions of IR
Spectra 07/23/21
Session 9
8
Important Spectral Regions in IR
…….
The fingerprint region (1500 – 600 cm-1).
 This region constitutes strong evidences for the identities

of cpds.
 Bands in this region are due to single bonds which are nearly

of similar energies;
 The absorption bands are thus composites of strong

interactions occurring between neighboring bonds, and

depend upon the overall skeleton structure of the particular
molecule;
 Exact interpretation of a spectrum is not however possible in

this region because of its complexity.

 In the fingerprint region a C-O-C stretching vib in ethers

and esters are found at about 1203 cm-1;

 The C-Cl stretching vib can be observed at 700 – 800 cm-1;

 Most inorganic groups such as sulfphate, phosphate, nitrate

and carbonate absorb at about 1200 cm-1.

07/23/21 Session 9
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Characterizing Compounds using IR
Spectra
IR characterization requires a systematic survey of the peak ID &
fingerprint regions and identify certain clues on the presence or
absence of certain group frequencies characterizing a particular
functional group.

Most important steps involve:

Look for some characteristic bands in the peak ID region (4000 -
1500 cm-1 ) & assign the cpd. to a particular functional group and
narrow down the possible structures;

Examine the fingerprint region (1500 - 600 cm-1 ) and the overall
spectrum to tentatively assign structures by matching peak for
peak.

Finally, describe the width & depth of absorption peaks as:

peak width  broad (br) and sharp (sh), and
peak depth  weak (w), medium (m), or strong (s).

Study and analyze;

The Correlation charts given in Figs. 29 & 30 showing characteristic ranges of
IR absorption for some typical bonds & types of bond vibrations, respectively.

10
Fig.29. Correlation Chart 1:
Typical IR Absorption Ranges of Common bonds

Short  Long

 Fig.30 Correlation Chart 2: General Regions of IR Spectrum
(Vibrational bands)
Keys:
 Blue colored bands refer to stretching vibrations, and
 Green colored band refer to bending vibrations
Group Frequencies
Note that, from the color scheme in Chart 2, stretching
absorptions are in the blue shaded region; bending absorptions in
the green shaded region.

More detailed descriptions are required for certain groups: e.g.

alkenes, arenes, alcohols, amines & carbonyl compounds.

Since most organic compounds have C-H bonds, a useful rule is that
absorption in the
 2850 - 3000 cm-1 is due to sp3 C-H stretching;
 above 3000 cm-1 is from sp2 C-H stretching or sp C-H stretching
if it is near 3300 cm-1.

Detailed information about the IR absorptions observed for various

bonded atoms and groups is presented in Table 1:.
[Table 1 Collection of IR absorptions data for some common functional
groups].
 General Trends in IR Absorption bands:
Stretching frequencies are higher than corresponding bending
frequencies (i.e., easier to bend a bond than to stretch/compress
it.)
Bonds to H atom have higher stretching frequencies than those to
heavier atoms.

Stretching frequencies of:

Triple bonds > Double bonds,
Double bonds > Single bonds (except for bonds to H atom).

Note that,
Complexity of the IR spectra in the 1450 - 600 cm-1
(fingerprint region) makes it difficult to assign all the absorption
bands
 because of existence of unique patterns in this region.
Absorption bands in the 4000 - 1450 cm-1 region are due to
stretching vibrations of diatomic units, (also known as group
frequency region).
Identifying Group Frequencies in IR
 The H-Stretching Frequency Range (3700 – 2700 cm-1)

In this range:
The H-X stretching vibrations are forming strong
absorption peaks;
The H atom being always the smaller atom than any other
atom forming a bond with it,
 the vibrational motion in H-X bond is largely due to the
H-atom;

 Thus, the st frequency due to the H-X bond is much

higher than that of any other bond;

 In addition, the vibrational interaction of H-X bond is

usually small;

07/23/21 Session 9
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The H-X absorption peaks:
Peaks b/n 3000-3100 cm-1 may be largely due to various O-H
& N-H stretching vibrations;
O-H bands are often broader and usually appear at higher
frequencies than N-H bands;
O-H bands are noticed only in the case of dilute non-polar
solvents;
H-bonding tends to broaden the O-H peaks and also move
them towards the lower wave numbers (i.e., longer ’s)
Aliphatic C-H vibration peaks occur in the range of 3000 –
2850 cm-1;
Any substituent that affects the C-H bond strength (e.g., Cl-
C-H) will cause a shift in the C-H Amax beyond 3000 cm-1;
The aldehydic C-H vibration (i.e., in H-C=O) forms a distinct
peak in the range of 2745 – 2710 cm-1;
Substituting D for H causes a shift to the lower wave number
by the factor of approx. 1/√2. (effect used to identify C-H
bonds);

07/23/21 Session 9
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Identifying Group Frequencies in IR ……..

The H-X absorption peaks:

Peaks in the range 2600 – 2550 cm-1 may be due to
presence of S-H;
Peaks in the range 2400 – 2350 cm-1 may be due to
presence of P-H;
Peaks in the range 2260 – 2090 cm-1 may be due to
presence of Si-H;

Triple-bond Absorption Range (2700 – 1850 cm-1):

 Triple bond peaks due to stretching vibrations appear:

At 2250 – 2225 cm-1 for –C ≡ N;

At 2180 – 2120 cm-1 for –N+ ≡ C;
At 2260 – 2190 cm-1 for –C ≡ C-

07/23/21 Session 9
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 Identifying Group Frequencies in IR …….
Double-bond Absorption Range (1950 – 1550 cm-1):
The carbonyl (CO) stretching vibration is characterized by
absorption throughout this region.

The absorption peaks at about 1700 cm-1 are due to the presence
of ketones, aldehydes, acids, amides and carbonates;

Absorption peaks in the 1770 – 1725 cm-1 region may be regarded

as resulting due to esters, acid chlorides or acid anhydrides.

Conjugation usually tends to lower the absorption peak by ~20

cm-1.

Impossible to determine the type of CO present in this region;

Examination of an additional spectral region is most essential for
clear cut identification.

07/23/21 Session 9
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Identifying Group Frequencies in IR …….
Note that,
a strong C-O-R stretching peak is obtained at about 1200
cm-1 in case of esters, while
a distinct H-C- peak is obtained just above 2700 cm-1 in case
of aldehydes;

Absorption peak located in the 1690 – 1600 cm-1 range arises

from C=C and C=N stretching vibrations; the structure of
olefins can be obtained by making use of such absorption
peaks.

Absorption peaks located in 1650 – 1450 cm-1 range provide

information about the presence of aromatic rings;

Aromatic cpds. with a low degree of substitution exhibit four

absorption peaks near 1600, 1580, 1500 and 1460 cm-1.

07/23/21 Session 9
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Identifying Group Frequencies in IR ……..
The fingerprint region (1500 – 600 cm-1).
This region constitutes strong evidences for the identities of cpds.
Bands in this region are due to single bonds which are nearly of
similar energies;

The absorption bands are thus composites of strong interactions

occurring b/n neighboring bonds, and depend upon the overall
skeleton structure of the particular molecule;

Exact interpretation of a spectrum is not however possible in this

region because of its complexity.

In the fingerprint region a C-O-C stretching vibration in ethers

and esters are found at about 1203 cm-1;

The C-Cl stretching vibrations can be observed at 700 – 800 cm-1;

Most inorganic groups such as sulfphate, phosphate, nitrate and

carbonate absorb at about 1200 cm-1.

20
Fig.31: A Correlation Chart for IR Spectroscopy
Table 2: Some easily recognizable IR Absorption
Patterns

07/23/21 Session 9
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Fig. 32 Assigning Group Frequencies to the
Compound
Fig. 33.Try to associate the spectrum below to any one of
the isomers following it.
Practice Problems on IR
Spectroscopy

Assignment # 3
 Find the Worksheets on IR Spectroscopy

and practice using them!!

(b) Quantitative Analysis

Quantitative analysis procedures using IR spectrometry

utilize Beer's Law.
Once the %T or A measurements are made, the data
reduction procedures are identical with those outlined
previously for UV/vis spectrophotometer.

The analyst should prepare just one standard solution to

which to compare the unknown using the ratio and proportion
scheme and determine the conc. by direct calculation or
prepare a series of standards and utilize a Beer's Law plot.

Reading the % T from the recorded IR spectrum for

quantitative analysis could however be a big challenge.

This and many other limitations with the IR technique make

quantitative analysis a difficult job for analysts.
End of Session 7